CN1168154A - Amorphous alkaline silicate compound - Google Patents

Amorphous alkaline silicate compound Download PDF

Info

Publication number
CN1168154A
CN1168154A CN96191455A CN96191455A CN1168154A CN 1168154 A CN1168154 A CN 1168154A CN 96191455 A CN96191455 A CN 96191455A CN 96191455 A CN96191455 A CN 96191455A CN 1168154 A CN1168154 A CN 1168154A
Authority
CN
China
Prior art keywords
weight
silicate compound
alkaline silicate
washing composition
acid
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN96191455A
Other languages
Chinese (zh)
Inventor
凯瑟林·施奈普
勒内一安德烈斯·阿蒂格·冈萨雷斯
卡特里·厄尔布斯
休伯特·弗里兹
曼弗雷德·格雷格
伯恩德·拉尔森
沃尔克·鲍尔
彼得·桑德库赫勒
威尔弗里德·拉赫斯
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of CN1168154A publication Critical patent/CN1168154A/en
Pending legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/08—Silicates
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D11/00—Special methods for preparing compositions containing mixtures of detergents
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D11/00—Special methods for preparing compositions containing mixtures of detergents
    • C11D11/02—Preparation in the form of powder by spray drying

Landscapes

  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Detergent Compositions (AREA)
  • Silicates, Zeolites, And Molecular Sieves (AREA)
  • Dental Preparations (AREA)

Abstract

Water-soluble builder substances are to be prepared for the partial or complete replacement of zeolith in washing or cleaning agents. In addition, said water-soluble builder substances are also to be capable of absorbing constituents of washing or cleaning agents which are liquid or waxy at the operating temperature. Thus extruded washing or cleaning agents and a process for producing them is to be prepared which contain the water-soluble builder substances to the extent where zeolith may be partly or completely excluded not only for application but also for processing reasons. These aims are achieved by spray-dried amorphous alkaline silicate compounds with secondary washing power and a mol ratio of M2O : SiO2 (M = alkaline metal) or between 1:1.5 and 1:3.3, containing anionic tensides in proportions of 0.5 to less than 30 wt.%.

Description

Amorphous alkaline silicate compound
The present invention relates to have amorphous alkaline silicate compound of auxiliary (sekundarwasch mogen) scourability, it can be used for the water soluble detergency promoter of washing composition or cleaning formulation.The invention still further relates to this alkaline silicate compound at washing composition or cleaning formulation, the washing composition of extruding or the application in the cleaning formulation, with and preparation method thereof.
There are some shortcomings usually in the washing composition or the cleaning formulation of modern dense form, owing to its imporosity has caused being insoluble in the aqueous solution, for example, lightweight spray-dried detergent of the prior art or cleaning formulation.Common washing composition or cleaning formulation are higher in its compactness, then more are insoluble in water.Usually as the zeolite of the washing assistant in washing composition or the cleaning formulation,, can cause the deterioration of its solubility property owing to its water-fast performance.
Amorphous alkaline silicate compound with auxiliary scourability can be used as the water-soluble quid pro quo that substitutes zeolite.
The water-soluble silicate that can obtain pulverous conventional hydration by spraying drying or roll-in drying to water glass solution, the moisture that wherein still contains 20% (weight) is (with reference to the Ullmanns chemical encyclopedia, nineteen eighty-two the 4th edition, the 21st volume, the 412nd page), the said products is sold for various uses.Therefore this powder has loose especially structure owing to be that spraying drying is made.Its bulk density is starkly lower than 700 grams per liters usually.
Can prepare particulate state alkalimetal silicate according to European patent application EP-A-0526978 with higher bulk density.Be solids content that the alkali metal silicate solutions of 30-53% (weight) is sent in the cylinder of heating wherein.This tube rotates around its longitudinal axis, and this has a plurality of bars that almost are stretched over contiguous inner wall of rotary drum.The wall temperature of cylinder keeps 150-200 ℃, is that the about 250 ℃ gas of 175-keeps above-mentioned drying process by feed temperature in cylinder.Median size by the prepared product of aforesaid method is the 0.2-2 millimeter.Above-mentioned desiccant gas preferably adds warm air.
European patent application EP-A-0542131 describes a kind of method, wherein can make at room temperature fully water-solublely, and its bulk density is the product of 500-1200 grams per liter, and dry preferred the use adds warm air.This method is to use to be had heated wall the cylinder shape moisture eliminator of (160-200 ℃) carries out.Make one have foliated tumbler around its longitudinal axis with the rotation of certain speed, making it is the silicate solutions of 40-60% (weight) by solids content, forming its free water content is the pseudo-plasticity material of 5-12% (weight), wherein implements drying process with adding warm air (220-260 ℃) stream.
Prepared water-soluble of a kind of method that is similar to European patent application EP-A-0526978 equally also described in the unpub so far in early days patent application P.4419745.4, amorphousness and particulate state alkalimetal silicate, however it contains silicic acid.Here so-called " amorphousness " is meant " x ray amorphousness ".This means that this alkalimetal silicate does not produce violent reflex action in the x-ray diffraction diagram, but one or more at the most wide maximum value, its width extent reaches the several years diffraction angle.Therefore, in electron diffraction test, can not produce and have the reflex action of violent electron diffraction.This can be construed to this material and have crystallite zone up to about 20 nanometers (maximum is 50 nanometers).
By to the spraying drying of sodium silicate solution, then grind, and last proceed compacting and spheroidizing when dewatering by abrasive after, can prepare granular amorphousness silicic acid sodium, this is a United States Patent (USP) 3,912,649,3,956,467,3,838,193 and 3,879,527 theme.The water content of the said products is about 18-20% (weight meter), and its bulk density is apparently higher than 500 grams per liters.
By European patent application EP-A-0561656 and known other alkalimetal silicate with auxiliary scourability of EP-A-0488868, described product is alkaline carbonate and the mixture with alkalimetal silicate of definite Q distribution.These products are by with sodium silicate solution (water glass solution), make powdered, anhydrous yellow soda ash carry out granulating.And dry and product that obtain, make this product have definite residual moisture content that is combined in the silicate.
German patent application DE-A-4406592 has disclosed absorbent alkali metal silicate salt mixture.It is that mode with multicomponent mixture exists, and is to make by with superheated vapour the aqueous compositions of multicomponent mixture being carried out spraying drying.This mixture can be used as the particularly carrier of tensio-active agent of fluid preparation.
European patent application EP-A-0219314 has introduced the particle of spray-dired high surfactant, it contain (a) 30-60% (weight) by alkylbenzene sulfonate and C 12-C 16Alkyl-sulphate is formed, its part by weight is 4: 1～1: 4 a mixture, and (b) alkalimetal silicate, and (a) weight ratio to (b) is 1.5: 1～6: 1.
European patent application EP-A-0651050 has described a kind of preparation method of agglomerate, wherein with a kind of salt, for example silicate or carbonate are with a kind of aqueous " binding agent " processing treatment that contains 20% (weight) silicate and at least 30% (weight) anion surfactant at least.
European patent EP .486592 has disclosed a kind of preparation method of high-density pressing materials, wherein the loose premixture of solid is squeezed into ropy under pressurized conditions.Therefore the loose pressing materials of above-mentioned solid comprises softening agent and/or lubricant, makes the deliquescing under pressurization and physical process condition of this premixture, can extrusion processing.After flowing out from the perforation mould, just shear action is in this system never again, and therefore the viscosity of this system can increase, so that can be by the size of predetermined in advance pressing materials, the ropy that shear extrusion goes out.Only know by International Patent Application WO-A-94/09111, must comprise component in the premixture that push and have the component of the fluidity energy that rises with structural viscosity.When only containing the component of structural viscosity in the premixture, because the effect of its tangible shear gradient makes it softening, so that almost be flow-like.Make the ropy that comes out from the perforation mould no longer have cutting performance.Thereby, also to add component with the fluidity energy that rises, when it improves at shear gradient, also can improve its plasticity, thereby guarantee the cutting performance of extruding ropy.The composition of most washing composition or cleaning formulation has structural viscosity.The fluidity that rises can make an exception especially.Usually the component that has the fluidity that rises in washing composition or cleaning formulation is to be used as the water-fast pure aluminium silicate of washing assistant and phosphoric acid salt surrogate, as zeolite.Push washing composition as can be known or cleaning formulation contains 19% (weight) zeolite (based on anhydrous active substance), the amorphousness silicic acid sodium of 12.5% (weight) yellow soda ash and 2.2% (weight) from International Patent Application WO-A-94/09111.Yet, and do not know, from the angle of technical process, this zeolite whether can part or even fully by water-soluble inorganic washing assistant amorphous alkaline silicate for example, institute replaces, they are with certain form application.Thereby show that some has the processing of alkaline silicate compound under water, high shear force and/or (slightly) temperature raising effect of auxiliary scourability can partly lose its auxiliary scourability.
One of task of the present invention is the water soluble detergency promoter that preparation is used for partly or entirely replacing washing composition or cleaning formulation mesolite, can improve the dissolving power of heavy washing composition or cleaning formulation thus especially.What in addition, above-mentioned water soluble detergency promoter also had washing composition under the processing temperature of being absorbed in or a sanitising agent becomes the ability of waxy composition by flow-like.Another task of the present invention provides a kind of washing assistant, it in addition in the course of processing, can not lose auxiliary scourability yet.Another task of the present invention is preparation squeezable washing composition or cleaning formulation and preparation method thereof, and including wherein that a certain amount of water soluble detergency promoter makes it not only still can both be partly or entirely without zeolite from preparation technology's angle from the application art angle.
The objective of the invention is aforesaidly, relate to the spray-dired amorphous alkaline silicate compound with auxiliary scourability, wherein M according to first embodiment 2O: SiO 2The molar ratio of (M is a basic metal) is 1: 1.5～1: 3.3, and contains 0.5% to the anion surfactant that is lower than 30% (weight).
The M of preferred amorphous alkaline silicate 2O: SiO 2The mol ratio of (M is a basic metal) is 1: 1.9-1: 3, and especially 1: 2.5.Wherein, pay the utmost attention to water glass and/or potassium silicate.From economic point of view, give special priority for water glass.But consider that from the application art angle because its extra high dissolution rate in water, suggestion is replaced sodium with potassio at least in part.For example, the composition of the alkalimetal silicate that can select for use is to contain the potassium component in the silicate, with K 2The O meter, its content is lower than 5% (weight).Preferred alkalimetal silicate is the mixture that contains alkaline carbonate, preferably contains yellow soda ash and/or salt of wormwood.The water-content of above-mentioned preferred amorphous alkaline silicate compound is 10-22% (weight), and is advisable with 12-20% (weight), is best with 14-19% (weight) especially.
Mixture according to the present invention is to make by the water in suspension liquid that contains alkalimetal silicate and anion surfactant is carried out spraying drying.Wherein form the alkaline silicate compound that its water content is 14-19% (weight).Particularly the suspension that is added with alkaline carbonate, especially yellow soda ash and/or salt of wormwood is in addition carried out spraying drying.
The anion surfactant that in alkaline silicate compound, is added, the preferably tensio-active agent of sulfonate type and/or sulfate type.Can pay the utmost attention to C as sulfonate surfactant 9-C 13Alkylbenzene sulfonate, ethylenic sulfonate, promptly by sulfonated alkene and hydroxyl sulfonated alkane, and the mixture of stilbene-4,4'-bis-(1-azo-3, 4-dihydroxy-benzene)-2,2'-disulfonate.For example, by a C with two strands terminal or internal fixing 12-C 18Strand alkene carries out sulfonation with gaseous sulfur trioxide, then above-mentioned sulfonation resultant is carried out the sulfonate that alkalescence or tart hydrolysis reaction make.Also can select sulfonated alkane for use, by C 12-C 18Paraffinic hydrocarbons carries out sulphur chlorination or sulphur oxygenizement, and is hydrolyzed or neutralizing effect and the sulfonate that makes.The sulfated surfactant that is suitable for can comprise by sulfuric acid monoester natural or that the synthetic primary alconol makes.As the basic vitriol of alkane (alkene), preferably C 12-C 18Fatty Alcohol(C12-C14 and C12-C18) is as coconut Fatty Alcohol(C12-C14 and C12-C18), tallow Fatty Alcohol(C12-C14 and C12-C18), lauryl alcohol, myristyl alcohol, hexadecanol or stearyl alcohol or C 10-C 20An alkali metal salt of the sulfate hemiester of oxo alcohol, especially its sodium salt, and half ester with secondary alcohol of above-mentioned chain length.In addition, also comprise the basic vitriol of alkane (alkene), wherein contain synthetic, the alkyl group of the straight chain that petrochemical processing makes with above-mentioned chain length.It has the compound similar decomposability made to the oil chemistry raw material.On washing process, particularly preferably be C 16-C 18The basic vitriol of alkane (alkene).With C 16-C 18The basic vitriol of alkane (alkene) is used in combination with low melting property aniorfic surfactant, especially with have low Krafft temperature point, and under low wash temperature, use together as having the incline aniorfic surfactant of gesture of low crystallization in ℃ scope of room temperature～40, be very favourable, machine washing composition especially.Therefore, in a preferable embodiment of the present invention, mixture contains the mixture of the fatty alkyl vitriol of short chain and long-chain, preferably C 12-C 14Fatty alkyl vitriol or C 12-C 18Fatty alkyl vitriol and C 16-C 18Fatty alkyl vitriol, especially C 12-C 16Fatty alkyl vitriol and C 16-C 18The mixture of fatty alkyl vitriol.But, in another preferred embodiment of the present invention, not only used saturated alkyl-sulphate, but also used its alkene chain length to be C 16-C 22Undersaturated alkenyl sulfate.Especially be C by its chain length 16Fatty Alcohol(C12-C14 and C12-C18) and its chain length C of dominant saturated sulfateization 18The mixture that dominant undersaturated sulfate Fatty Alcohol(C12-C14 and C12-C18) is formed is best.For example, HD-Ocenol (R)Solid-state or the liquid fatty alcohol mixture of (the applicant's product).Wherein alkyl-sulphate is 10 for the weight ratio of alkenyl sulfate: 1-1: 2, and be advisable with about 5: 1～1: 1.
The anion surfactant that is suitable for can also comprise by U.S. Pat-3234258 or US-5075041 prepared 2, the 3-alkyl-sulphate, it also is that the name that the Shell Oil Co. produce is called DAN (R)Commodity.
Can also use C straight chain or side chain of ethoxylation with 1-6 moles of ethylene oxide 7-C 21The sulfuric acid monoester of alcohol for example, has the C of the 2-methyl branch of average 3.5 moles of ethylene oxide (EO) 9-C 11Alcohol or have the C of 1-4 mole EO 12-C 18Fatty Alcohol(C12-C14 and C12-C18).Yet because the sulfuric acid monoester of above-mentioned alcohol has higher foam ability, so its content in washing composition is very low, has only 1-5% (weight) approximately.
In a preferable embodiment of the present invention, mixture contains 15-80% (weight) alkalimetal silicate, 1-25% (weight) preferably is lower than the aniorfic surfactant of 20% (weight), and 10-22% (weight), preferred 12-19% (weight), the preferably water of 14-19% (weight).Find, when anion surfactant surpasses 25% (weight), sometimes even when the time, will cause the reduction of the auxiliary scourability of whole washing composition above 20% (weight).I infer-do not require and am limited to present principles, promptly contain the mixture dissolving so rapidly of high-content anion surfactant, so that before water hardness salt is removed by silicate, passive interaction has taken place between water hardness salt and anion surfactant.
In another embodiment of the invention, mixture of the present invention contains 15-50% (weight), preferably the alkalimetal silicate of 20-40% (weight); 30-70% (weight), the preferably alkaline carbonate of 40-65% (weight); 1.5-15% (weight), the anion surfactant (the preferably basic vitriol of alkylbenzene sulfonate and/or alkane (alkene)) of preferred 2-12% (weight), and the water of 12-19% (weight).
Above-mentioned alkaline silicate compound can also contain the component of other washing composition or cleaning formulation, and preferred content is lower than 10% (weight), especially is no more than 5% (weight).These components can comprise, neutral salt for example, and as sodium sulfate or vitriolate of tartar, burnt hair inhibitor or nonionic surface active agent are as alkyl poly glucoside.
Alkaline silicate compound according to the present invention is for being in a liquid state under common service temperature or the component of waxy washing composition or cleaning formulation has tangible receptivity.Though under the situation of not adding aniorfic surfactant, alkaline silicate compound also can absorb a certain amount of liquid composition.But find,, will improve the receptivity of alkaline silicate compound, and improve its loose performance by adding aniorfic surfactant.In a preferable embodiment of the present invention, the alkaline silicate compound that contains anion surfactant according to the present invention has the receptivity of liquid towards component, and the receptivity than the alkaline silicate compound of the same amount that does not add aniorfic surfactant improves 20% at least.Preferred especially mixture of the present invention even improve 30% at least than the receptivity of the liquid towards component of the corresponding alkali metal silicate composite of the same amount that does not contain aniorfic surfactant, even advantageously improve 50%.
The present invention relates to spray-dired alkaline silicate compound in another embodiment, it uses liquid composition, comprises in the scope of the invention being in a liquid state under service temperature to the component of waxy washing composition or cleaning formulation, carries out aftertreatment.According to alkaline silicate compound of the present invention absorbent suitable liquid composition comprise nonionic surface active agent, cationic surfactant and/or froth suppressor are as silicone oil and paraffin oil.Particularly preferably be nonionic surface active agent, as oxyalkylated, preferred ethoxylation and/or ethoxylation and propenoxylated aliphatic C 8-C 22Alcohol.Wherein particularly including primary alconol with 8-18 carbon atom and average 1-12 moles of ethylene oxide of each mol of alcohol (EO), wherein the alcohol radical group can be the methyl branch that has on second position straight chain or preferred, the group that perhaps can contain straight chain and methyl branch, be form of mixtures, as the oxo process alcohol groups form of common existence.Similarly, particularly preferably be the alcohol ethoxylate of straight chain base of the alcohol of natural source with 12-18 carbon, for example, coconut alcohol, palmityl alcohol, tallow Fatty Alcohol(C12-C14 and C12-C18) or oleyl alcohol, and each mol of alcohol on average has 2-8 EO.Preferred ethoxylated alcohol is the C that 3EO or 4EO are arranged 12-C 14Alcohol has the C of 7EO 9-C 11Alcohol has the C of 3EO, 5EO, 7EO or 8EO 13-C 15Alcohol has the C of 3EO, 5EO or 7EO 12-C 18Alcohol, and their mixture.The C that 3EO is for example arranged 12-C 14The pure and mild C that 5 EO are arranged 12-C 18The mixture of alcohol.Above-mentioned ethoxylation degree statistical average value representation can be an integer or mark for concrete product.The preferred alcohols ethoxylate have narrow homology distribute (ethoxylate of close limit, NRE).In addition, nonionic surface active agent also can be the Fatty Alcohol(C12-C14 and C12-C18) that has more than 12 EO.For example, the tallow Fatty Alcohol(C12-C14 and C12-C18) that has 14EO, 25EO, 30EO or 40EO.
The nonionic surface active agent of another kind of preferred use, what it can use separately or be used in combination with other described nonionic surface active agent is alkoxylate, preferably ethoxylation or ethoxylation and the propenoxylated fatty acid alkyl ester that 1-4 carbon atom preferably arranged at its alkyl chain, especially fatty acid methyl ester, as described at Japanese patent application Jp 58/217598, or prepared according to the method for International Patent Application WO-A-90/13533.
Compare with the alkaline silicate compound that does not contain aniorfic surfactant, initial spray-dired mixture of the present invention has stable auxiliary scourability when being processed into washing composition.This mixture particularly of the present invention shows to have stable auxiliary washing function, and its surface is subjected to hydrophobic treatment thereafter, preferably handles with nonionic surface active agent.
Alkaline silicate compound of the present invention is spray-dried preparation.By containing the whole components of alkaline silicate compound, (except the liquid that mixture is used with aftertreatment is formed) aq suspension carries out spraying drying in the particularly preferred method, and the preparation alkaline silicate compound.
Mixture of the present invention in another embodiment of the invention is to prepare by mixing the aqueous formulation of forming according to the method for German patent application DE-A-4406592 with superheated vapour spraying drying multicomponent.
The composition of the above-mentioned alkaline silicate compound that makes and washing composition or cleaning formulation is carried out subsequent disposal.Said process can be implemented by usual method.For example in mixing-prilling granulator, mix or spray, carry out heat treated in case of necessity.
Above-mentioned amorphous alkaline silicate mixture with auxiliary scourability can be as additive when preparation powdery or detergent granules or cleaning formulation; or when preparation detergent granules or cleaning formulation, week make integral part, preferably in granulation and/or compression process, use.According to used method in its production, the bulk density of alkaline silicate compound for example is, the 50-850 grams per liter.On the contrary, be the 300-1200 grams per liter according to the bulk density of washing composition of the present invention and/or sanitising agent, be preferably the 500-1000 grams per liter, and the amount that wherein contains silicate composite of the present invention is preferably 5-50% (weight), more preferably 10-40% (weight).Can be by any known method preparation, as mixing, spraying drying, granulation, compacting, as roll-in and extruding.The method that is suitable for is various ingredients, and for example spray-dried component and granulation component and/or extruding component are mixed together mutually.Also can carry out the processing of spraying drying or granulation composition with nonionic surface active agent, particularly ethoxylized fatty alcohol compound tense by any usual method.Particularly in granulation or pressing method, other anion surfactant of Cun Zaiing is preferably with spraying drying in case of necessity, and the composite form of granulation or extruding is used, and they are in method or as blending ingredients or as the additive behind other particle.Equally also be possible also favourable; according to prescription; thereafter with the composition of other discrete washing composition and/or cleaning formulation; for example carbonate, Citrate trianion or citric acid; or other multi-carboxylate or poly carboxylic acid, polymeric carboxylate salt; zeolite and/or layered silicate; for example lamellated crystallization pyrosilicate; be added in the composition of spraying drying, granulation and/or extruding, this composition is aqueously handled to the waxy composition with being under service temperature of nonionic surface active agent and/or other in case of necessity.In a preferable methods, can also form or subsequently processing is carried out on the surface of all compositions the part of washing composition and/or cleaning formulation, to reduce particulate viscosity and/or to improve solvability.The surface-modifying agent that is suitable for is known in the prior art.Except other surface-modifying agents that is suitable for, granuliform zeolite, silicic acid, uncrystalline silicon hydrochlorate, lipid acid or soap, calcium stearate for example, wherein preferential especially is the mixture of zeolite and silicon-dioxide, particularly zeolite is 1: 1 o'clock to the weight ratio of silicon-dioxide at least, perhaps the mixture of zeolite and calcium stearate.
Particularly preferred embodiment of the present invention is extruding washing composition and/or the sanitising agent of bulk density greater than 600 grams per liters, it contains aniorfic surfactant in extrudate, nonionic surface active agent in case of necessity, and the amorphous alkaline silicate compound of the above-mentioned type.The washing composition of these extruding and/or cleaning formulation can be used known pressing method, and particularly the method with European patent EP-B-0486592 is prepared.Wherein, be lower than under 200 bar pressures, solid, loose premixture are squeezed into ropy, the ropy that the extruded hole mold pressing is gone out with shear is sheared by predetermined granular size then.Then, above-mentioned plasticity, also moistening in case of necessity rough pressing materials carries out another shaping or procedure of processing, carries out drying treatment then.Alkaline silicate compound of the present invention is to be used for above-mentioned premixture.
The alkaline silicate compound that contains aniorfic surfactant in preparation extruding washing composition and/or cleaning formulation process is not only in application facet, and at the alkaline silicate compound that all is better than not containing anion surfactant aspect the preparation.Find, use in the pressing method of the alkalimetal silicate carbonate mixture that does not contain anion surfactant, should not interrupt, because under static state, extruding mixture can lose its plasticity-and the too fast safety problem that consequently has of sliding when Restarter.This problem is by using the alkaline silicate compound that contains aniorfic surfactant, especially the alkaline silicate compound that contains aniorfic surfactant and carbonate, replacement does not conform to the alkaline silicate compound of aniorfic surfactant and can solve.
Final washing composition or cleaning formulation can contain following ingredients in addition.
These compositions comprise tensio-active agent, at first are aniorfic surfactant, and nonionic surface active agent in case of necessity.Also can comprise cationic surfactant, amphoterics or zwitterionics.
The aniorfic surfactant of the sulfonate type that is suitable for comprises alkylbenzene sulfonate mentioned above, ethylenic sulfonate, and sulfonated alkane.But the ester class (sulfonated ester) of alpha-sulfo-fatty acid, hydrogenated coconut lipid acid for example, the α-sulfonation methyl ester of palm nuclear lipid acid or tallow fatty acids also is suitable for.In addition, other suitable anion surfactant is that ester by alpha-sulfo-fatty acid alkyl ester decomposes prepared alpha-sulfo-fatty acid or its disalt.In its industrial-scale production as forming single salt of alpha-sulfo-fatty acid alkyl ester with the aqueous mixture of limited amount disalt.Two salts contgs of this tensio-active agent are usually less than 50% (weight) of aniorfic surfactant mixture, for example generally are to be lower than 30% (weight).
The other aniorfic surfactant that is suitable for can also be the sulfonated glycerin fatty acid ester, comprising one ester, diester and three esters, with and composition thereof.They are the esterifications by the lipid acid of single glycerine and 1-3 mole, and perhaps the transesterification of the glycerine by triglyceride level and 0.3-2 mole makes.
The tensio-active agent of the sulfate type that is suitable for is the sulfuric acid monoester, 2 of the primary alconol of above-mentioned natural and synthetic source, 3-alkyl-sulphate, and the derivative of the alkoxylate of sulfuric acid monoester in case of necessity, particularly ethoxylation.Other aniorfic surfactant that is suitable for is the salt of alkyl sulfo-succinic acid, they also are known as sulfosuccinate or sulfosuccinic ester, they represent sulfo-succinic acid and alcohols, especially an ester and/or the diester of the Fatty Alcohol(C12-C14 and C12-C18) of Fatty Alcohol(C12-C14 and C12-C18), particularly ethoxylation.Preferred sulfosuccinate contains C 8To C 18Fatty alcohol radical, or its mixture.Particularly preferred sulfosuccinate contains a fatty alcohol radical, and it is by the ethoxylized fatty alcohol deutero-.Be nonionic surface active agent in itself.Wherein, its Fatty Alcohol(C12-C14 and C12-C18) group is particularly preferred by the ethoxylized fatty alcohol deutero-sulfosuccinate with narrow homology distribution.Basic succsinic acid of alkane (alkene) or its esters that 8-18 carbon atom similarly, also can preferably be arranged on the basic chain of its alkane (alkene) with the basic succsinic acid of alkane (alkene).
The soap class that also can contain 0.2-5% (weight) except aniorfic surfactant, washing composition or cleaning formulation.Suitable soap class is the saturated fatty acid soap, for example, lauroleate, the nutmeg hydrochlorate, palmitate, stearate, hydrogenant eruciate and docosoic, and by natural acid, as coconut fatty acid, palm-kernel hydrochlorate or tallow fatty acid deutero-soap class mixture.
Aniorfic surfactant and soap class can exist with its sodium salt, sylvite or ammonium salts, and as organic bases, exist as the solubility salt of Monoethanolamine MEA BASF, diethanolamine or trolamine.This aniorfic surfactant preferably exists with its sodium salt or potassium salt form, particularly exists with its sodium-salt form.
In one embodiment of the invention, washing composition or cleaning formulation especially push the aniorfic surfactant that washing composition or cleaning formulation contain 10-30% (weight).Advantageously, wherein preferably contain 3% (weight) at least, especially with the sulfated surfactant of at least 5% (weight).In the preferred embodiments of the invention, based on the aniorfic surfactant total amount, contain 15% (weight) at least in this washing composition or the cleaning formulation, the sulfated surfactant of preferred 20-100% (weight).
Preferred nonionic surfactants is aforementioned alkoxylate, and especially the alcohols with 8-18 carbon atom of ethoxylation and every mol of alcohol have an average 1-12 moles of ethylene oxide (EO).
The oxyalkylated fatty acid alkyl ester of mentioning equally in front also can use.
In addition, as other nonionic surface active agent, can be RO (G) also with its chemical formula xAlkyl glycoside.Wherein, R represents that has a 8-12, the uncle's of preferred 12-18 carbon atom aliphatic group, it can be straight chain or methyl branch, methyl branch is particularly arranged on the second position.G represents to have the glucose unit of 5 or 6 carbon atoms, especially represents glucose.Oligomeric degree x represents the distribution of monoglycosides and oligosaccharides glycosides, and it is the numerical value between the 1-10.
The nonionic surface active agent of amino oxide type, N-coco group alkyl-N for example, N-dimethylamino base oxide and N-tallow base alkyl-N, N-dihydroxy ethyl amino oxide, and Marlamid also all is suitable.The consumption of above-mentioned nonionic surface active agent preferably is not higher than the consumption of used ethoxylized fatty alcohol, particularly is not higher than its half amount.
Other tensio-active agents that are suitable for can be the polyhydroxy fatty acid amides with following chemical formula (I)
Figure A9619145500131
R wherein 2CO represents an aliphatic acyl with 6-22 carbon atom, R 3Represent hydrogen, contain the alkyl or the hydroxyalkyl of 1-4 carbon atom, and [Z] expression contains the multi-hydroxy alkyl of the straight or branched of 3-10 carbon atom and 3-10 hydroxyl.Above-mentioned polyhydroxy fatty acid amide is a known substance, normally passes through reducing sugar ammonia, and alkylamine or alkanolamine carry out the reductibility ammonification, carry out acylations with lipid acid, fatty acid alkyl ester or lipid acid chlorination thing thereafter and make.
Washing composition of the present invention or cleaning formulation contain nonionogenic tenside, and its content is 0.5-15% (weight), preferably 2-10% (weight).
Except the amorphous alkaline silicate mixture that auxiliary scourability is arranged, washing composition can also contain other washing assistant and common washing assistant.For example, can contain in the washing composition common washing assistant as, phosphoric acid salt, zeolite and crystalline layer silicate.Used synthetic zeolite is the fine crystallization shape preferably, and contains combination water.The for example zeolite A, X zeolite and the zeolite P that select for use also can be the mixtures by zeolite A, X and/or P.Zeolite can be with spray-dired powder type, or even to use as the form of producing the undried of still moist stable suspension by it.When zeolite used with the form of suspensoid, suspensoid can contain a spot of nonionogenic tenside that adds as stablizer.For example, count the ethoxylation C of 1-3% (weight) with 2-5 ethylene oxide group with zeolite 12-C 18Fatty Alcohol(C12-C14 and C12-C18) has the C of 4-5 ethylene oxide group 12-C 14The isotrideyl alcohol of Fatty Alcohol(C12-C14 and C12-C18) or ethoxylation.Also can use zeolite suspensoid and zeolite powder.The zeolite powder that is suitable for has the median size (volume distributed median: measured by Coulter Counter method) that is less than 10 microns, and preferably contains 18-22% (weight), more preferably the combination water of 20-22% (weight).Zeolite content in washing composition or the cleaning formulation can be lower than 40% (weight) (based on anhydrous active substance).
By a particularly preferred embodiment of the present invention, this washing composition or cleaning formulation contain the zeolite of 10-16% (weight) (based on anhydrous active substance), and the alkaline silicate compound of the present invention of 10-30% (weight).
According to another particularly preferred embodiment of the present invention, this washing composition or cleaning formulation contain the zeolite of 0-5% (weight) (based on anhydrous active substance), and the alkaline silicate compound of the present invention of 15-40% (weight).In addition, zeolite not only can carry out coextrusion processing, and can partially or completely zeolite be joined in washing composition or the cleaning formulation in next step after pressing steps.The washing composition or the cleaning formulation that contain the extrudate of no zeolite in its core are preferred especially.
Crystalline layer silicate and/or common phosphoric acid salt also can be used as the surrogate of zeolite, but only to be used for washing composition or cleaning formulation on a small quantity, particularly its amount is at most 10% (weight) to phosphoric acid salt.
The crystalline layer silicate that is suitable for particularly has NaMSi xO 2x+1YH 2The crystalline layer silicate of O chemical formula, the M in the formula represents sodium or hydrogen, and x represents the numerical value of 1.9-4, and Y represents the numerical value of 0-20, and the preferred value of x is 2,3 or 4.European patent application EP-A-0164514 described this crystalline layer silicate.The preferred crystalline layer silicate that is equivalent to above-mentioned chemical formula is that wherein M represents that sodium, x value are 2 or 3.Particularly preferably be β-water glass and δ-water glass Na 2Si 2O 5YH 2O.But the content of above-mentioned crystalline layer silicate is not to be higher than 10% (weight) in extrudate of the present invention, preferably is lower than 8% (weight), preferably 5% (weight) at the most.
The polymeric polycarboxylate can be used as washing assistant.The polymeric polycarboxylic acid ester that is suitable for can be the sodium salt of polyacrylic acid or polymethyl acrylic acid, and for example, its relative molecular weight is 800-150000 (based on acid).Polycarboxylate, the especially vinylformic acid of the copolymerization that is suitable for and the multipolymer of methacrylic acid, and the multipolymer of acrylic or methacrylic acid and toxilic acid.The multipolymer of particularly suitable comprises the multipolymer of vinylformic acid and toxilic acid.It contains the vinylformic acid of 50-90% (weight) and the toxilic acid of 50-10% (weight).Its relative molecular weight based on free acid, is 5000～200000, and is preferred 10000～120000, preferably 50000～100000.In addition, terpolymer also is particularly preferred, for example, according to the acrylate of German patent application DE-A-4300772 and maleate and vinyl alcohol or vinyl alcohol derivatives as monomeric terpolymer or according to the acrylate of German patent DE-C-4221381 and 2-alkylallyl sulfonate and sugar derivatives as monomeric terpolymer.The multipolymer of Shi Yonging can be disclosed according to German patent application DE-A-4303320 and P4417734.8 in addition, with propenal and vinylformic acid/acrylate as monomer or propenal and ethene acetic ester as monomeric multipolymer.
Other spendable organic altogether washing assistants can be poly carboxylic acid its sodium salts preferably for example, for example citric acid, hexanodioic acid, succsinic acid, pentanedioic acid, tartrate, saccharic acid, aminocarboxylic acid, itrile group three acetic acid (NTA), as long as can use from economic angle is operable, and their mixture.Preferred salt is the salt salt and composition thereof of citric acid, hexanodioic acid, succsinic acid, pentanedioic acid, tartrate, saccharic acid for example of poly carboxylic acid.
Other spendable builder materials comprise oxidation resultant and/or its water-soluble salt of the many dextran that contain carboxylic group.The preparation method of described material of International Patent Application WO-A-93/08251 or described this material of International Patent Application WO-A-93/16110 for example.
Similarly, known poly aspartic acid and its salt with and derivative also can be used as builder material.
The builder material of Shi Yonging can be a polyacetal in addition, describes according to European patent application EP-A-0280223, and it can and contain 5-7 carbon atom and the multi-hydroxy carboxy acid's of at least 3 hydroxyls reaction make by dialdehyde.The polyacetal that is suitable for can be by dialdehyde, as oxalic dialdehyde, and glutaraldehyde, terephthalic aldehyde and composition thereof and multi-hydroxy carboxy acid, prepared as glyconic acid and/or glucose enanthic acid.
Content at final washing composition or the common washing assistant in the cleaning formulation can be 0.5-20% (weight), is preferably 2-15% (weight).
What detergent addition also can contain other can be by the effective constituent of wash away grease in the fabric.When handling contaminated textile fabric with the washing composition that contains the greasy effective constituent of above-mentioned solubilized of the present invention, its effect is obvious especially.The preferred greasy effective constituent of solubilized comprises for example non-ionic fiber ether, as contain methylcellulose gum and first hydroxy propyl cellulose based on the propoxyl group of 15-30% (weight) methoxyl group of non-ionic fiber ether and 1-15% (weight), and the polymkeric substance of the polymkeric substance of phthalic acid well known in the prior art and/or terephthalic acid and derivative thereof, particularly ethylene terephthalate and/or polyoxyethylene glycol terephthalate or its negatively charged ion and/or nonionic modified derivative.
In addition, washing composition can also contain and can improve the deliquescent composition of heavy particle.International Patent Application WO-A-93/02176 and German patent application DE-A-4203031 have described mentioned component and application thereof.Preferred mentioned component can be the Fatty Alcohol(C12-C14 and C12-C18) that every mole of Fatty Alcohol(C12-C14 and C12-C18) has 20-80 moles of ethylene oxide (EO).For example, has the tallow Fatty Alcohol(C12-C14 and C12-C18) of 30EO and the tallow Fatty Alcohol(C12-C14 and C12-C18) of 40 EO is arranged.Also can be Fatty Alcohol(C12-C14 and C12-C18) with 14 EO, with and relative molecular weight be the polyoxyethylene glycol of 200-2000.In water, can generate H 2O 2The compound as SYNTHETIC OPTICAL WHITNER in, the Sodium peroxoborate monohydrate acquires a special sense.Other available SYNTHETIC OPTICAL WHITNER also comprise as sodium perborate tetrahydrate, SPC-D, pyrophosphate peroxide, Citrate trianion perhydrate, and can generate H 2O 2Persalt or peracid, cross nonane diacids or two as peroxybenzoic acid salt, peroxide phthalate, two and cross the dodecyl acid.Bleach levels in the washing composition is about 5-25% (weight), especially 10-20% (weight), wherein preferred perborate monohydrate.Percarbonate also is preferred effective constituent.But percarbonate does not preferably carry out co-extrusion process, but adds in case of necessity subsequently.
To obtain improved bleaching effect in order under 60 ℃ or lower temperature, washing, can in preparation, to add bleach activator.Bleach activator is and H 2O 2Form the N-acyl compounds or the O-acyl compounds of organic peracid, N preferably, N '-four acylations diamines to (chain triacontanol base oxygen) benzene sulfonate, in addition, can also be carboxylic acid anhydride and polyol ester, as glucose five acetic esters.Other known bleach-activating agents are the acetylizad mixtures as described Sorbitol Powder of european patent application document EP-A-0525239 and mannitol.The content that contains the bleach-activating agent in the washing composition of SYNTHETIC OPTICAL WHITNER, based on final washing composition, 1-10% (weight) normally, and be advisable with 3-8% (weight).Particularly preferred bleach-activating agent is N, N, N ', N '-tetra acetyl ethylene diamine (TAED), 1.5-diacetyl-2, the mixture of 4-dioxo six hydrogen-1,3,5-triazines (DADHT) and acetylizad Sorbitol Powder-mannitol.
It also is favourable adding froth suppressor in washing composition.The froth suppressor that is suitable for for example contains high-load C 18-C 24The soap class of the natural source of lipid acid or synthetic source.The froth suppressor of the nonsurfactant class that is suitable for for example, organopolysiloxane and and microfine, the mixture of the silica of silanization, and paraffin in case of necessity, wax, Microcrystalline Wax and with the mixture of silanization silica or distearyl acyl group oxalamide.Also can use the mixture of different foam inhibitor, for example, the mixture of silicone, paraffin or wax.The froth suppressor that is suitable for particularly contains the froth suppressor of silicone and/or paraffin, is combined in granulous, on the carrier substance of water-soluble or water-dispersion.Wherein, the mixture of paraffin and distearyl acyl group oxalamide preferably.
Spendable enzyme comprises proteolytic enzyme, lipase, amylase, cellulase or its mixture.The enzyme of particularly suitable is by bacterial strain or fungi, plants the active substance that the enzyme of enzyme (Humicola insolens) gained is urged as Bacillus subtilus (Bacillus subtilis), lichenoid form bacillus (Bacilluslicheniforrmis), streptomyces griseus (Streptomyces griseus) and corruption.The proteolytic enzyme of subtilyne type is preferred, and the proteolytic enzyme that derives from slow genus bacillus (Bacillus lentus) is preferred especially.Can also use mixed enzyme, for example by proteolytic enzyme and amylase, or the mixture of proteolytic enzyme and lipase or proteolytic enzyme and cellulase or cellulase and lipase or proteolytic enzyme, amylase and lipase or proteolytic enzyme, lipase and cellulase, wherein particularly preferably be the mixture that contains proteolytic enzyme and/or lipase.In some cases, also available peroxidase or oxydase.Enzyme can be adsorbed on the carrier substance and/or be encapsulated in the involucrum material, with the decomposition that prevents that it is too early.The content of enzyme, enzyme mixture or enzyme granulate is about 0.1～5% (weight) in final washing composition, preferably 0.1～2% (weight).
Stablizer especially for crossing compound and enzyme, is the salt of polyphosphonic acid, 1-hydroxyl ethane-1 particularly, 1-di 2 ethylhexyl phosphonic acid (HEDP), Diethylenetriamine pentamethylene phosphonic acids (DETPMP) or ethylenediamine tetramethylene phosphonic acid.
Washing composition or cleaning formulation also can contain other enzyme stabilizers, for example contain the sodium formiate of 0.5-1% (weight).In addition, can also add proteolytic enzyme, it is stable with soluble calcium salt, and based on this enzyme, its calcium contents is about 1.2% (weight).Preferably add boron compound, for example boric acid, boron oxide compound, borax and other alkali metal borate, as ortho-boric acid (H 3BO 3), metaboric acid (HBO 2) and pyroboric acid (tetraboric acid H 2B 4O 7).
The burnt hair inhibitor can make that isolating dirt remains on the suspension washing lotion from fabric, so that can prevent its burnt hair look effect.Most of organic natural water-soluble colloids are applicable to above-mentioned effect, for example the salt of the water soluble salt of carboxylic acid polyalcohol, colloid, gelatin, starch or cellulosic ether sulfonic acid or ether carboxylic acid, the perhaps salt of starch or cellulosic tart sulfuric ester.The water miscible polymeric amide that contains acidic-group also is applicable to above-mentioned purpose.In addition, the starch preparation of solubility and other above-mentioned starch products also are suitable for, degraded starch for example, starch aldehyde etc.Polyvinylpyrrolidone also is applicatory.Also can use ether of cellulose, carboxy methyl cellulose (Na salt) for example, methylcellulose gum, hydroxy alkyl cellulose and mixed ether thereof, as methyl hydroxyl ethyl cellulose, methyl hydroxy propyl cellulose, methyl carboxylic cellulose and composition thereof, and polyvinylpyrrolidone, its consumption is 0.1-5% (weight) based on washing composition for example.
Above-mentioned washing composition or cleaning formulation can contain as the derivative of the diaminostilbene disulfonic acid of whitening agent or its an alkali metal salt.The whitening agent that is suitable for is 4,4 '-two (2-anilino-4-morpholino-1,3,5-triazines base-6-amino) stilbene-2,2 '-salt of disulfonic acid or the compound of homogeneous structure, morpholino base is wherein substituted by diethanolamino, methylamino-, anilino or 2-methoxyl group ethylamino.
In addition, the whitening agent of the diphenyl benzene vinyl-type of above-mentioned replacement can have, for example 4,4 '-two (2-sulfo group styryl)-phenylbenzene, 4,4 '-two (2-chloro-3-sulfo group styryl)-phenylbenzene, or an alkali metal salt of 4-(4-chloro-styrene base)-4 '-(2-sulfo group styryl)-phenylbenzene.In addition, also can use the mixture of above-mentioned whitening agent.
Except containing alkaline silicate compound, it also contains alkaline carbonate in preferred embodiments, above-mentioned washing composition or cleaning formulation can also contain other inorganic salts, other amorphous alkaline silicates of the above-mentioned type, and other alkali metal carbonate of the above-mentioned type.Other the inorganic salts that can be considered as composition is a neutral salt, with the vitriol of sodium and/or potassium salt form, can be its muriate in case of necessity.
Certainly, above-mentioned washing composition or sanitising agent can also contain washing composition or cleaning formulation contained pigment and spices usually.
EXAMPLE Example 1: the preparation of alkaline silicate compound
According to alkaline silicate compound C of the present invention 1-C 4, and contrast mixture VC makes by aqueous suspension is carried out usual spraying drying respectively.The composition of mixture (with % (weight) expression) is as follows:
C 1 ??C 2 ??C 3 ?C 4 ?VC
Amorphousness disilicic acid sodium 28.1 ??28.1 ??27.3 ?24.65 ?29.0
Yellow soda ash 53.4 ??53.4 ??51.7 ?46.75 ?55.0
C 12-C 18Alkyl-sulphate (sodium salt) 3.0 ??- ??- ?- ?-
C 12Alkylbenzene sulfonate (sodium salt) - ??3.0 ??6.0 ?15.0 ?-
Water 15.5 ??15.5 ??15.0 ?13.6 ?16.0
Embodiment 2: the receptivity of alkaline silicate compound (irritate and drench test)
According to alkaline silicate compound C of the present invention 1-C 4Receptivity be to use nonionic surface active agent to compare with the receptivity of the contrast mixture VC that uses equivalent, nonionogenic tenside is the C with 5 EO by 80% (weight) 12-C 18The C with 3 EO of Fatty Alcohol(C12-C14 and C12-C18) and 20% (weight) 12-C 14Fatty Alcohol(C12-C14 and C12-C18) is formed.Press the receptivity of DINISO 787 mensuration nonionic surface active agent, wherein replace the oleum lini of defined with above-mentioned nonionic surface active agent.In order to measure, the sample of weighing is placed on the square position.Then, splash into 4 or 5 nonionic surface active agent with drop-burette at every turn.After each the adding, nonionic surface active agent is rubbed in the pulverulent material of smearing with scraper.The adding nonionic surface active agent that keeps forms aggregate until above-mentioned nonionic surface active agent and pulverulent material.At this moment, just begin to add 1 nonionic surface active agent at every turn, and be rubbed into scraper.After forming the pulpiness thing, just stop to add nonionic surface active agent.
Above-mentioned mashed prod can make it spread out and not break or broken loosing, and still sticks on the square position.At this moment, just can read the titer of the nonionic surface active agent of emitting, and be converted into the milliliter number of per 100 gram nonionic surface active agent that sample added by drop-burette.Test-results is as follows:
The milliliter number of the nonionic surface active agent of per 100 gram carriers
?C 1 ?????????????????97
?C 2 ?????????????????110
?C 3 ?????????????????128
?C 4 ?????????????????130
?VC ?????????????????57
Embodiment 3: extrusion performance
Prepare following extruded material E of the present invention by International Patent Application WO-A-94/02047 1～E 4And contrast extruded material VE.Detergent material E 1-E 4Extrusioning mixture can under without any the difficulty that relates to technology, push.And simultaneous test product VE just just can prepare under the situation that its preparation process is no more than 60 minutes break period.The composition of above-mentioned each extruded material is as shown in table 1.The bulk density of each extruded material is 750～780 grams per liters.Extruded material not only of the present invention, and the extruded material of simultaneous test all has the good solubility energy: in flushing or dissolubility test, only present a spot of residue.
Table 1
E 1～E 4Composition (% (weight) meter) with EV:
????E 1 ??E 2 ??E 3 ???E 4 ??EV
C 9-C 13Alkylbenzene sulfonate ????11.5 ??11.5 ??11.5 ???11.5 ??11.5
C 12-C 18Alkyl-sulphate ????10.5 ??10.5 ??10.5 ???10.5 ??10.5
C with 7EO 12-C 18Alcohol ????4.0 ??4.0 ??4.0 ???4.0 ??4.0
C 12-C 18Fatty acid soaps ????1.0 ??1.0 ??1.0 ???1.0 ??1.0
Relative molecular weight is 400 polyoxyethylene glycol ????1.5 ??1.5 ??1.5 ???1.5 ??1.5
Zeolite (anhydrous active substance) ????19.0 ??19.0 ??19.0 ???19.0 ??19.0
Vinylformic acid-maleic acid (sodium salt) ????6.0 ??6.0 ??6.0 ???6.0 ??6.0
Alkaline silicate compound C 1 ????14.0 ??- ??- ???- ??-
Alkaline silicate compound C 2 ????- ??14.0 ??- ???- ??-
Alkaline silicate compound C 3 ????- ??- ??14.0 ???- ??-
Alkaline silicate compound C 4 ????- ??- ??- ???14.0 ??-
Alkaline silicate compound C 5 ????- ??- ??- ???- ??14.0
Perborate-hydrate ????21.0 ??21.0 ??21.0 ???21.0 ??21.0
Phosphonate ????0.7 ??0.7 ??0.7 ???0.7 ??0.7
Sodium salt ????1.5 ??1.5 ??1.5 ???1.5 ??1.5
Water and salt from solution Surplus Surplus Surplus Surplus Surplus

Claims (13)

1. have the spray-dired of auxiliary scourability, amorphous alkaline silicate compound, wherein M 2O: SiO 2(M is a basic metal) mol ratio is 1: 1.5～1: 3.3, it is characterized in that, contains 0.5～be lower than the anion surfactant of 30% weight.
2. according to the alkaline silicate compound of claim 1, it is characterized in that it contains the alkalimetal silicate of 15-80% weight, the anion surfactant of 1-25% weight, the preferred aniorfic surfactant of 20% weight at the most and the water of 10-22% weight.
3. according to the alkaline silicate compound of claim 1 or 2, it is characterized in that it contains 15-50% weight, the alkalimetal silicate of preferred 20-40% weight; 30-70% weight, the alkaline carbonate of preferred 40-65% weight; 1.5-15% weight, the anion surfactant of preferred 2-12% weight, the preferably water of basic vitriol of alkylbenzene sulfonate and/or alkane (alkene) and 12-19% weight.
4. according to the alkaline silicate compound one of among the claim 1-3, it is characterized in that, the receptivity of liquid component than equivalent, is not contained the receptivity high at least 20% of the alkaline silicate compound of aniorfic surfactant, preferably at least 30%, preferably at least 50%.
5. according to the alkaline silicate compound one of among the claim 1-4, it is characterized in that use liquid component, promptly the composition of washing composition or cleaning formulation, particularly nonionogenic tenside carry out aftertreatment.
6. according to the preparation method of the amorphous alkaline silicate compound one of among the claim 1-5 with auxiliary scourability, it is characterized in that, the aqueous suspension solution of the whole compositions that contain alkaline silicate compound is carried out spraying drying and makes this mixture.
7. according to the method for claim 6, it is characterized in that, the water preparation of multicomponent mixture is carried out spraying drying with superheated vapour.
8. according to the method for claim 6 or 7, it is characterized in that,, especially handle with nonionic surface active agent the washing composition or the cleaning formulation composition of the alkaline silicate compound of spray-dried processing with liquid.
9. according to the alkaline silicate compound one of among the claim 1-5 with auxiliary scourability, the application in washing composition or cleaning formulation, wherein the latter is spray-dried, granulation, compacting, prepares as roll-in or extruding or through blending means.
10. washing composition or cleaning formulation, based on anhydrous active substance, it contains the zeolite of 10-16% weight, and the alkaline silicate compound one of among the claim 1-5 of 10-30% weight.
11. washing composition or cleaning formulation wherein based on anhydrous active substance, contain the zeolite of 0-5% weight, the alkaline silicate compound one of among the claim 1-5 of 15-40% weight.
12. bulk density is the extruding washing composition or the cleaning formulation of 600 grams per liters, wherein contain negatively charged ion and optional nonionogenic tenside, and amorphous alkaline silicate, it is characterized in that amorphous alkaline silicate compound that it one of contains among the claim 1-5 with auxiliary scourability.
13. the preparation method of washing composition or cleaning formulation, wherein solid, loose premixture, be squeezed into ropy being lower than under 200 bar pressures, and the ropy that goes out from the perforation mold pressing is sheared by predetermined granular size with shear, mouldable, still moistening in case of necessity thick extrudate is carried out another forming process processing, then carries out drying then, it is characterized in that, in above-mentioned premixture, add according to the amorphous alkali metal silicate salt mixture one of among the claim 1-5.
CN96191455A 1995-01-18 1996-01-09 Amorphous alkaline silicate compound Pending CN1168154A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19501269A DE19501269A1 (en) 1995-01-18 1995-01-18 Amorphous alkali silicate compound
DE19501269.0 1995-01-18

Publications (1)

Publication Number Publication Date
CN1168154A true CN1168154A (en) 1997-12-17

Family

ID=7751688

Family Applications (1)

Application Number Title Priority Date Filing Date
CN96191455A Pending CN1168154A (en) 1995-01-18 1996-01-09 Amorphous alkaline silicate compound

Country Status (15)

Country Link
US (2) US6191096B1 (en)
EP (1) EP0804529B1 (en)
JP (1) JPH10512321A (en)
KR (1) KR19980701494A (en)
CN (1) CN1168154A (en)
AT (1) ATE190645T1 (en)
CZ (1) CZ226797A3 (en)
DE (2) DE19501269A1 (en)
ES (1) ES2144721T3 (en)
HU (1) HUP9702001A3 (en)
PL (1) PL324033A1 (en)
PT (1) PT804529E (en)
RU (1) RU2168542C2 (en)
SK (1) SK96297A3 (en)
WO (1) WO1996022349A1 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1649993B (en) * 2002-04-26 2010-05-26 宝洁公司 Spray drying process and compositions formed thereby

Families Citing this family (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19501269A1 (en) * 1995-01-18 1996-07-25 Henkel Kgaa Amorphous alkali silicate compound
DE19525378A1 (en) * 1995-07-12 1997-01-16 Henkel Kgaa Amorphous alkali silicate compound
DE19529908A1 (en) * 1995-08-15 1997-02-20 Henkel Kgaa Process for the preparation of an amorphous alkali silicate with impregnation
DE19533790A1 (en) * 1995-09-13 1997-03-20 Henkel Kgaa Process for the preparation of an amorphous alkali silicate with impregnation
DE19700775A1 (en) * 1997-01-13 1998-07-16 Henkel Kgaa Process for the production of washing and cleaning active surfactant granules containing anionic surfactants
DE19953792A1 (en) * 1999-11-09 2001-05-17 Cognis Deutschland Gmbh Detergent tablets
EP1489934B1 (en) * 2001-09-13 2010-05-26 Daniel James Plant Flexible energy absorbing material and methods of manufacture thereof
DE10161597B4 (en) 2001-12-14 2005-10-20 Celanese Chem Europe Gmbh Process for the purification of alicyclic alcohols
GB0221430D0 (en) * 2002-09-16 2002-10-23 Ineos Silicas Ltd Powder coating compositions
DK1729734T3 (en) * 2004-03-30 2008-06-16 Smithkline Beecham Corp Spray-dried pharmaceutical preparations
US20060178289A1 (en) * 2004-07-20 2006-08-10 Enrique Hernandez Multifunctional material compositions and methods
US20060019865A1 (en) * 2004-07-20 2006-01-26 Enrique Hernandez Methods and compositions of multifunctional detergent components
US20070161539A1 (en) * 2006-01-12 2007-07-12 Enrique Hernandez Method of regulating degree of polymerization of an alkali metal silicate in solution using pH
US20150182960A1 (en) * 2013-12-31 2015-07-02 Ecowater Systems Llc Zeolite regeneration

Family Cites Families (40)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3234258A (en) 1963-06-20 1966-02-08 Procter & Gamble Sulfation of alpha olefins
US3838193A (en) 1971-03-13 1974-09-24 Kawasaki Heavy Ind Ltd Method of treating nitrogen oxide generating substances by combustion
US3879527A (en) 1971-10-28 1975-04-22 Huber Corp J M Alkali metal polysilicates and their production
US3838192A (en) 1971-10-28 1974-09-24 Huber Corp J M Production of alkali metal polysilicates
US4006110A (en) * 1971-11-30 1977-02-01 Colgate-Palmolive Company Manufacture of free-flowing particulate heavy duty synthetic detergent composition
US3956467A (en) 1974-06-07 1976-05-11 Bertorelli Orlando L Process for producing alkali metal polysilicates
JPS6018717B2 (en) * 1976-05-18 1985-05-11 ライオン株式会社 Granular detergent composition
JPS6059280B2 (en) * 1976-07-09 1985-12-24 ライオン株式会社 Method for producing granular detergent composition
US4129526A (en) 1977-07-14 1978-12-12 The Lion Fat & Oil Co., Ltd. Granular detergent compositions and a process for producing same
JPS58217598A (en) 1982-06-10 1983-12-17 日本油脂株式会社 Detergent composition
DE3413571A1 (en) 1984-04-11 1985-10-24 Hoechst Ag, 6230 Frankfurt USE OF CRYSTALLINE LAYERED SODIUM SILICATES FOR WATER SOFTENING AND METHOD FOR WATER SOFTENING
AU597909B2 (en) 1985-10-09 1990-06-14 Procter & Gamble Company, The Granular detergent compositions having improved solubility
DE3706036A1 (en) 1987-02-25 1988-09-08 Basf Ag POLYACETALS, METHOD FOR THE PRODUCTION THEREOF FROM DIALDEHYDES AND POLYOLCARBONIC ACIDS AND USE OF THE POLYACETALS
DE3914131A1 (en) 1989-04-28 1990-10-31 Henkel Kgaa USE OF CALCINATED HYDROTALCITES AS CATALYSTS FOR ETHOXYLATION OR PROPOXYLATION OF FATTY ACID ESTERS
DK0486592T3 (en) 1989-08-09 1994-07-18 Henkel Kgaa Preparation of compacted granules for detergents
DE4010533A1 (en) 1990-04-02 1991-10-10 Henkel Kgaa Prodn. of high-density detergent granules
US5075041A (en) 1990-06-28 1991-12-24 Shell Oil Company Process for the preparation of secondary alcohol sulfate-containing surfactant compositions
DK0488868T3 (en) 1990-11-30 1996-03-18 Rhone Poulenc Chimie Builder agent based on alkali metal silicates for detergent compositions
ES2083690T3 (en) 1991-07-02 1996-04-16 Crosfield Joseph & Sons SILICATES.
DE4124701A1 (en) 1991-07-25 1993-01-28 Henkel Kgaa METHOD FOR THE PRODUCTION OF SOLID DETERGENT AND CLEANING AGENT WITH HIGH SHOCK WEIGHT AND IMPROVED SOLUTION SPEED
ATE155165T1 (en) 1991-07-31 1997-07-15 Ausimont Spa METHOD FOR INCREASING THE BLEACHING EFFECTIVENESS OF AN INORGANIC PER SALT
DE4134914A1 (en) 1991-10-23 1993-04-29 Henkel Kgaa DETERGENT AND CLEANING AGENT WITH SELECTED BUILDER SYSTEMS
IT1252682B (en) 1991-11-13 1995-06-23 Vomm Impianti & Processi Srl PRODUCT IN HIGH SPECIFIC WEIGHT GRANULES, PARTICULARLY AS A POWDER DETERGENT ADDITIVE AND METHOD FOR ITS OBTAINING
DE4221381C1 (en) 1992-07-02 1994-02-10 Stockhausen Chem Fab Gmbh Graft copolymers of unsaturated monomers and sugars, process for their preparation and their use
DE4203031A1 (en) 1992-02-04 1993-08-05 Henkel Kgaa METHOD FOR THE PRODUCTION OF SOLID DETERGENT AND CLEANING AGENT WITH HIGH SHOCK WEIGHT AND IMPROVED SOLUTION SPEED
DE4203923A1 (en) 1992-02-11 1993-08-12 Henkel Kgaa METHOD FOR PRODUCING POLYCARBOXYLATES ON A POLYSACCHARIDE BASE
FR2688798B1 (en) 1992-03-20 1994-10-14 Rhobb Poulenc Chimie BUILDER AGENT BASED ON SILICATE AND A MINERAL PRODUCT.
DE4216775A1 (en) * 1992-05-21 1993-11-25 Henkel Kgaa Powdery surfactant mixture
DE4235646A1 (en) 1992-10-22 1994-04-28 Henkel Kgaa Process for the production of extrudates that are active in washing and cleaning
DE4300772C2 (en) 1993-01-14 1997-03-27 Stockhausen Chem Fab Gmbh Water-soluble, biodegradable copolymers based on unsaturated mono- and dicarboxylic acids, process for their preparation and their use
DE4303320C2 (en) 1993-02-05 1995-12-21 Degussa Detergent composition having improved soil carrying power, process for its preparation and use of a suitable polycarboxylate therefor
EP0651050A1 (en) 1993-11-03 1995-05-03 The Procter & Gamble Company Surfactant agglomerate particle
DE4400024A1 (en) * 1994-01-03 1995-07-06 Henkel Kgaa Silicate builders and their use in detergents and cleaning agents as well as multi-component mixtures for use in this field
DE4405511A1 (en) * 1994-02-22 1995-08-24 Henkel Kgaa Detergent with amorphous silicate builder substances
DE4406592A1 (en) * 1994-03-01 1995-09-07 Henkel Kgaa Improved multi-substance mixtures based on water-soluble alkali silicate compounds and their use, in particular for use as builders in detergents and cleaners
DE4415362A1 (en) * 1994-05-02 1995-11-09 Henkel Kgaa Process for the production of silicate builder granules with increased bulk density
DE4417734A1 (en) 1994-05-20 1995-11-23 Degussa Polycarboxylates
DE4419745A1 (en) 1994-06-06 1995-12-07 Henkel Kgaa Granulated water-soluble silicic acid-containing alkali silicate
DE19501269A1 (en) * 1995-01-18 1996-07-25 Henkel Kgaa Amorphous alkali silicate compound
DE19525378A1 (en) * 1995-07-12 1997-01-16 Henkel Kgaa Amorphous alkali silicate compound

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1649993B (en) * 2002-04-26 2010-05-26 宝洁公司 Spray drying process and compositions formed thereby

Also Published As

Publication number Publication date
EP0804529A1 (en) 1997-11-05
JPH10512321A (en) 1998-11-24
RU2168542C2 (en) 2001-06-10
HUP9702001A2 (en) 1998-03-02
DE19501269A1 (en) 1996-07-25
HUP9702001A3 (en) 1999-03-01
EP0804529B1 (en) 2000-03-15
ATE190645T1 (en) 2000-04-15
CZ226797A3 (en) 1998-03-18
WO1996022349A1 (en) 1996-07-25
SK96297A3 (en) 1998-01-14
US6191096B1 (en) 2001-02-20
US20020002130A1 (en) 2002-01-03
DE59604687D1 (en) 2000-04-20
US6458755B2 (en) 2002-10-01
KR19980701494A (en) 1998-05-15
PL324033A1 (en) 1998-05-11
ES2144721T3 (en) 2000-06-16
PT804529E (en) 2000-09-29

Similar Documents

Publication Publication Date Title
CN1065268C (en) Washing agent with amorphous silicate builder substances
CN1168154A (en) Amorphous alkaline silicate compound
CN1135203A (en) Silicates builders and there use in washing or cleaning agents and multi-substance mixtures for use in this field
JPH11512463A (en) Method for producing impregnated amorphous alkali metal silicate
CN1045310C (en) Detergent compositions
CN1155298A (en) Liquid washing or cleaning product with bleaching powder
CN1259163A (en) Additive granules for moulded bodies having a detergent and cleaning action
JP2837325B2 (en) Detergent composition and method for producing the same
CN1257535A (en) Detergent shaped body with enhanced dissolving properties
CN1111594C (en) Make the method for detergent composition
CN1140466A (en) Multi-substance mixtures based on water-soluble alkali silicate compound and their use
CN1190430A (en) Amorphous alkali silicate compound
JP2002502457A (en) Granular detergent
CN1681912A (en) Detergent compositions
EP2252676B1 (en) Spray-dried washing or cleaning products
JPH10509993A (en) Detergent composition
CN1276006A (en) Method for manufacturing washing and detergent particulates
CN1273598A (en) Method for producing stabile and rapidly dissolving washing detergent tablets
CN1063481C (en) Process for the production of a detergent composition
JP3875412B2 (en) Method for atomizing nonionic surfactant composition and method for producing granular detergent composition using the same
HU218141B (en) Impregnated amorphous alkaline silicates and process for producing thereof
JPH09504046A (en) Process for producing wash-active or clean-active extrudates with improved redispersibility
DE19936614B4 (en) Process for the preparation of a detergent
CN1289651C (en) Detergent compositions containing potassium carbonate and process for preparing them
JP4108199B2 (en) Method for producing granular detergent composition

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C02 Deemed withdrawal of patent application after publication (patent law 2001)
WD01 Invention patent application deemed withdrawn after publication